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Studies on the Reactivity of a Labile Tungsten Acetonitrile Complex

不稳定钨乙腈配合物的反应活性研究

基本信息

批准号：
10640536
负责人：
SAKABA Hiroyuki
金额：
$ 1.98万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

The reactivities of highly reactive complexes cis-Cp^*W(CO)_2(L)Me (1, L=McCN ; 2, L=py) towards a variety of reagents such as isocyanides, thiophenes, hydrosilanes, and hydrido (hydrosilyl) complexes were examined.(1) Acetonitrile complex 1 reacted with isocyanide to give acetonitrile-substitution and CO insertion products, whose ratio varied substantially depending upon the reaction temperature and isocyanide concentration. Its unusually high reactivity to the insertion reaction as an alkyl carbonyl tungsten complex was demonstrated by the facile formation of the insertion product even at-60℃. (2) The reaction of 1 with thiophene resulted in the highly selective α-C-H bond activation to give a 2-thienyl complex. (3) Pyridine complex 2 reacted with primary and secondary silanes to produce base-stabilized hydrido (silylene) complexes via Si-H bond activation and 1, 2-H migration, and the reactivity studies of the silylene complexes with hydrosilanes revealed their novel reactivity to afford silylene exchange products and base-stabilized silyl (silylene) complexes. (4) The reaction of 1 with a hydrido (hydrosilyl) rhenium complex gave a hydrido- and silylene-bridged Re-W heterobimetallic complex, and its photolysis led to intramolecular C-H bond activation to form a novel silenyl-bridged heterobimetallic complex.A molybdenum analogue of 2 was also prepared and subjected to reaction with hydrosilanes to afford base-stabilized hydrido (silylene)molybdenum complexes. The reaction of the silylene complex with a primary silane gave redistribution products of the silane in addition to a base-stabilized silyl (silylene) complex.

研究了高活性配合物cis-Cp^*W（CO）_2（L）Me（1，L=McCN ; 2，L=py）与异腈、噻吩、硅氢化物和硅氢化物的反应活性。(1)乙腈配合物1与异腈反应得到乙腈取代和CO插入产物，其比例基本上取决于反应温度和异腈浓度。在-60 ℃下也能容易地形成插入产物，证明了它作为烷基羰基钨配合物对插入反应具有异常高的反应活性。(2)1与噻吩的反应导致高度选择性的α-C-H键活化，生成2-噻吩基配合物。(3)吡啶配合物2通过Si-H键活化和1，2-H迁移与伯硅烷和仲硅烷反应生成碱稳定的亚硅基配合物，并与氢硅烷反应，得到亚硅基交换产物和碱稳定的亚硅基配合物. (4)1与含氢硅桥铼钨配合物反应，得到含氢硅桥铼钨配合物，其光解导致分子内C-H键活化，形成新型的硅桥铼钨配合物; 2的钼类似物与含氢硅反应，得到碱稳定的含氢硅桥铼钨配合物.甲硅烷基络合物与伯硅烷的反应除了碱稳定的甲硅烷基（甲硅烷基）络合物之外还得到硅烷的再分布产物。